Use of mobile catalysts in effecting chemical reactions



Aug. 15, 1950 T. B. HUDSON usE oF MOBILE cATALYsTs 1N EEEECTING CHEMICAL REACTIONS 5 Sheets-Sheet 1 Filed Oct. 14, 1947 Aug. 15, 1950 1:3. HUDSON 2,518,474

usE oF MoBILE cATALYsTs 1N EFFECTING cREMIcAL REACTIONS Filed Oct. 14, 1947 5 Sheets-Sheet 2 BF'3 AND PROPANE MAKE UP 53 REFRIG TIO lai-'3 AND 64 RRORANE 3 58 REFRIGERAT N 54 RFB RRORANE SOLVENT 6| POLYMER EP3 a SOLVENT RECOVERY PROCESSES REACTION CHAMBER BUTENES v SOLVENT A .INVENTOR THOMAS BA HUDSON 4BY s ATTORN YS Aug. l5, 1950 1:5. HUDSON use oF MOBILE cATALYsTs 1N EFFECTING CHEMICAL REACTIONS 5 Sheets-Sheet 5 Filed oct, 14, 1947 INVENTOR.

THOMAS B. HUDSON Mmym A T TORNEVS Patented Aug. l5, 1950 USE OF MOBILE CATALYSTS IN EFFECTING CHEMICAL REACTIONS Thomas B. Hudson, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application October 14, 1947, Serial No. 779,785

3 Claims.

This invention relates to improvements in catalytic processes. More particularly it relates to novel methods of bringing mobile catalysts into contact with reactants. It has particular relevance to organic reactions such as hydrocarbon conversions.

This application is a continuation-in-part of my copending application, Serial No. 453,265, led August 1, 1942, issued October 14, 1947 as U. S. Patent 2,429,161.

The use of ycatalysts has come to be of primary importance in industry. Catalysts may greatly accelerate the rate of reaction for many processes so that either a much more rapid conversion at a given temperature is obtained, or a much lower temperature may be used to accomplish a given conversion. In fact in many cases, catalysts of one kind or another have made possible the carrying out of reactions which previously had been believed impossible. While catalytic action cannot cause a reaction to occur which is thermodynamically impossible, it may be the only means of obtaining a practical rate of reaction for a given conversion. Utilization of elevated temperatures frequently cannot be relied on due to shifts in equilibrium concentrations or d-ue to the occurrences of undesired side reactions. Many reactions which will not take place at practicable temperature levels with any measurable speed, may occur almost quantitatively at reasonable temperatures in the presence of suitable catalysts.

In the hundred years since Berzelius rst recognized the existence of certain reactions which were promoted by substances not changed during the reaction, and suggested the use of the term catalysis for describing the forces involved, the search for effective catalystic materials has commanded the attention of a great segment of the technical world. Since the turn of the century, the successful results of these investigatiom have given rise to numerous new industries, as well as providing greatly improved methods for the older industries.

The petroleum industry may be taken as one outstanding example. Whereas fifteen to twentyiive years ago non-catalytic processes were utilized almost exclusively in all fields of petroleum refining, the trend now is toward catalytic processes, which are rapidly replacing older methods with results which are more satisfactory not only in increased eciency but also in procucing entirely new products. Present day needs call for high-octane gasoline, and various other fuels having special requirements. Aviation fuels in particular must now be prepared by blending almost pure individual hydrocarbons or hydrocarbon types in order to meet the demand for fuels which will readily respond to specic operating conditions. Olshoots from the petroleum industry, such as the production of synthetic rubbers, call for preparing very pure single hydrocarbons for use as raw materials.

Not only is the chemical composition of the catalytic material of importance in attaining specific results in chemical conversions, but its physical form, activation treatments, impurities, methods of contacting with reactants, reactivation processes, etc., all exert their influences on the co-urse of the conversions being catalyzed. The particular products and yields thereof obtained are also dependent to a great extent on such reaction conditions as pressure, temperature, time of contact between reactants and catalyst, etc. Careful control of all these variables is required for production of the optimum quantities and quality of products. Organic conversions are particularly susceptible to the effects of these various factors, due to the numerous side reactions which can occur.

One of the most important influences on the course of catalyzed reactions, and frequently one of the most diicult to control, is temperature. Most of such reactions are either highly endothermic or highly exothermic, and maintenance of the desired range of temperature is a major operating difculty. The activity of a catalyst for a definite conversion is usually of economic signi-cance only within a fairly narrow temperature range, and a particular process using that catalyst must obviously be operated within the active range. This condition is shown by the great change in the degree of conversion usually occurring with relatively small temperature changes.

Thus, in the case of endothermic reactions, the temperature drop which normally occurs may be so pronounced that the rate of conversion will rapidly decrease to an uneconomic level. In the case of exothermic reactions, a rise in temperaturenormally occurs which, if not controlled in some way, will rapidly bring the temperature to a point at which undesirable side reactions occur. In fact, such side reactions may frequently become the predominant reaction at temperatures only relatively slightly above those required for the desired conversions. Or, the principal reaction may be lcaused to proceed too rapidly, in

which case the reaction rate and temperature bel come uncontrollable with undesirable or even disastrous results. Accordingly, the careful control of temperature within narrow limits throughout a reaction zone for either endothermic or exothermic reactions is not only highly desirable but is ordinarily a necessity.

Many methods have been offered for the control of temperatures in catalytic conversions, usually involving complicated apparatus designs whereby indirect heat transfer is utilized in connection with portions of catalytic materials so small as to allow suicient heat to pass from or into the catalyst mass to accomplish the desired results. For example, particles of solid catalyst have been packed into relatively small tubes so that no portion of the catalyst is more than say one inch from a tube wall, and a number of such tubes connected in parallel, with a heat transfer medium being circulated about the exterior of the tubes. An alternative method has been to provide a system of coils or the like within a catalyst mass so that a heating or cooling medium, as required, may be circulated throughout the catalyst bed. Similar arrangements have been provided for reaction vessels employing moving catalysts. However, these methods have not been able to compensate fully for the low thermal conductivity of the usual catalysts. Furthermore, the surface of the tubes or other elements through which the heat transfer takes place, is at a temperature appreciably different from that generally prevailing in the reaction zone. This is disadvantageous, particularly with endothermic reactions where, in the case of hydrocarbon conversions for example, cracking, coke formation and other reactions take place on the superheated surfaces, which causes loss of materials and fouling of equipment.

Other methods proposed for compensating for heat or reaction include superheating of reactants involved in endothermic processes above optimum temperatures, or the converse, that is insuicient preliminary heating of exothermic reactants. The inefficiencies of such methods are obvious. Catalyst poisoning may sometimes occur to an increased extent at either lowered or increased temperature.

Probably the most common method of bringing solid catalysts into contact with reactants is to place the catalyst in a reaction chamber, and pass the reactants therethrough at the desired now rate, temperature, and pressure. However, in many cases, it has been found useful to cause the solid catalyst particles to move through the reaction zone. Also in the case of gaseous or liquid catalysts, the catalyst is frequently passed through the reaction zone. Such catalysts, whether solid, liquid, or gaseous, which are passed through a reaction zone are referred to herein as mobile or fluent catalysts. They may be passed either concurrently with or countercurrently to the reactant, depending upon the reactions being catalyzed, the catalyst, and other variables.

It is an object of this invention to provide novel catalytic processes. Another object is to provide improved methods of operating catalytic systems, particularly those employing mobile catalysts. Another object is to enable a more delicate control of catalyzed organic reactions, particularly hydrocarbon conversion. A further object is to provide improved methods of contacting mobile catalysts with reactants. A further object is to provide for the control of catalyzed. reactions with respect to temperature and/or products obtained. Yet another object is to permit controlled variation in the quantity and/or activity of catalyst present at all points in a reaction zone. A still further object is to provide for the introduction of one or more catalysts into a reaction zone at a plurality of points. Another object is to provide for the concurrent or countercurrent flow of catalyst thus introduced relative to the iiow of reactants. Another object is to correlate the introduction of catalyst with certain reaction conditions in an exact manner so as to compensate, at least in part, for change in temperature and/ or change in concentration of reactants, or other reaction conditions. Yet another object is to effect an endothermic reaction at substantially constant temperature throughout an elongated reaction zone. A further object is to provide for reactivating catalysts which have become deactivated in such processes so that the reactivated catalyst may be re-introduced into contact with reactants. Other objects and advantages of the invention will become apparent from the following disclosure.

My invention is essentially a method for carefully controlling catalytic processes by the multipoint addition of catalyst, specifically correlated with reaction conditions. Specific methods of operating are disclosed which are especially adapted for given types of conversions. These different methods, while each employing the introduction of catalyst into a reaction zone at a plurality of points, are not at all to be considered as exact equivalents inasmuch as each is particularly designed to give optimum results for the given application, as will be more fully explained. I am aware that catalytic materials have occasionally in the past been described as being introduced into a reaction zone at more than one point. Such disclosures, however, have been vague, indefinite, and most unenlightening as to the purposes involved and exact results accomplished. I have found specific relationships between catalyst introduction and reaction conditions, and have devised novel methods of correlating the various factors involved whereby new and highly useful results are accomplished, as will be apparent from the detailed teachings lhereinbelow set forth.

From one point of view, the invention may be considered as comprising three principal operational modiflcations. A first modification has to do with catalysts which are miscible with one or more reactants, either by virtue of mutual solubility or because of small particle size of the catalyst allowing its suspension in reactants. Such a suspension may be in a more or less stable form,

' or in a relatively separable form in which the catalyst is maintained in suspension by means of turbulent flow, static charges, etc. Finally divided solid catalysts are frequently suspended in gaseous reactants and passed through a zone mained under desired reaction conditions. Such catalysts have been called fluid catalysts, which is in actuality a misnomer. However, they do often pass at the same rate of flow as the reactants and the entire mixture may be handled more or less as a single fluid. As is well known in the art, the term fluid when applied to powdered solid catalysts includes the suspension of same in reactants under conditions of straightthrough flow, hindered settling, or even in fluidized beds. Accordingly, I may define "i'luid catalysts broadly to include not only gaseous and liquid catalysts, but also finely divided solids suspended in reactants. A second modification involves catalysts which are immiscible with reactants undergoing treatment, with the catalyst tions.

passing concurrently with the reactants through the reaction zone, generally at a rate dierent than the rate of flow of reactants. A third modification relates to catalytic materials which are non-miscible with reactants wherein the catalyst after being introduced at a plurality of points subsequently moves countercurrent to the reactants. In some cases there is a, combination of the modifications, in which at least one reactant passes countercurrently to at least one other reactant, in which case the catalyst will move concurrently with one reactant and countercurrently to another reactant.

The choice of operating method, and the manner of applying that method, will of course be based on the type of catalyst, reaction, and other factors. However, the choice of points for introduction of the catalyst and the rate at which catalyst is introduced at each point is correlated with change in temperature, change in concentration of reactants, etc., so as to compensate for such changes, as will now be more fully described.

By the use of my invention I may so interrelate the various factors such as temperature; flow rate of reactants, diluents, and catalysts; catalyst activity; time of -contact between reactants and catalyst; etc.; as to provide a most complete and delicate control over the nature and extent of all reaction at all points in the reaction zone.

As pointed out above, temperature control is possibly the major problem in carrying out vexothermic and endothermic reactions. The present invention provides methods for maintain- .ing proper reaction velocity in the face of increasing or decreasing temperature.

In the case of an endothermic reaction, the catalyst may be introduced at a plurality of points spaced in the direction of flow of reactants for concurrent flow therewith. The amount of catalyst is smallest in the rst portion of the reaction zone, and largest in the last portion of the zone, due to the incremental additions of catalyst which occur long the path of ow. The temperature at the outlet of the reaction zone is considerably lower than at the inlet because the endothermal reaction takes up heat. The amount of catalyst added at each point is chosen so as` to provide sucient `additional catalytic activity to maintain the rate of reaction in spite 4of the lowered temperature existing at that point. Thus, even though under ordinary conditions the rate of reaction at a temperature, say 50 or 100 F., lower than the optimum reaction temperature would be several times less,

resulting in much lowered conversion inthe latter portions of the reaction zone, the additional catalyst compensates at least partially vfor the lowered temperature and may maintain substantially constant conversion throughout the zone if added in suicient quantity at each point. In

supplying heat to the endothermic conversion by means of hot catalyst in carefully regulated amounts, as will be described in more detail hereinafter.

Another manner of utilizing this invention for endothermic reactions involves multipoint addi-I tion of catalyst with subsequent countercurrent ow relative to the reactants. This may be done especially if the catalyst used undergoes very rapid deactivation at the given reaction condi- In this case, the rate of introduction and zone.

-duced at the latter (earlier, with respect to reactants) points of the reaction zone. The total activity is quite limited, and smaller here than at subsequent points. As the reactants pass on through the zone, they contact smaller quantities of total catalyst, but the catalyst contacted has greater activity. The deactivated catalyst also has a diluent eiect, and a unit volume of reactants passes through the rst portions of the reaction zone more rapidly than it does through the last portions. Flow of reactants continues countercurrent to the ilow of catalyst until just before leaving the reaction zone they come in contact with a relatively small quantity of cata.- lyst having very high activity. The increasing catalyst activity thus encountered by the reactants as they flow enable the reaction rate to be maintained in spite of the decreasing temperature caused by the endothermic nature of 4the reaction. The increments of catalyst added at the points of lowest temperature may, if necessary, be larger than those added `at the points of higher temperatures, the quantity added, rate of addition and rate of ilow through the reaction zone always being so chosen and related as to compensate at least in part for the variation of ref action rate with temperature.

Alternatively or additionally, catalyst regenerated at a high; temperature may be used in such quantities as to maintain reaction temperature constant or to minimize the extent of temperature drop.

An ex'othermic reaction may be handled in a somewhat different manner, but with the same end in view, namely the control of catalyst activity and contact time between catalyst and reactants so as to compensate, in part at least, for variation of rate of reaction with temperature. Generally, the most satisfactory control is obtained by use of countercurrent flow of reactants and catalyst introduced multipoint. Reactants rst are contacted with a relatively large volume of catalyst, the ratio of catalyst activity to volume of reactants being greatest at this point and progressively decreasing in the direction of reactant ow, while the temperature correspondingly increases. At the higher temperature levels, less catalyst activity is encountered, so that reaction velocity may be maintained as nearly constant as desired. Near the exit from the reaction zone, the reactants are contacted with the smallest quantity of catalyst, this quantity, however, being suiiicient to maintain the desired rate of reaction. The advantages of operating in this manner may readily be seen by contrasting with prior methods wherein either the heat of reaction must be removed by difficult means heretofore discussed, or; if the temperature is allowed to increase, contact-with equal increments of catalyst combined with the higher temperatures causes greatly increased `reaction rates.

Another method of controlling exothermic reactions which is particularly, although not eziclusively adapted for use with catalysts which become rapidly deactivated, is the concurrent flow of multipoint-introduced catalyst. In such usage, a nrstportion of catalystis introduced either lalong with the reactant feed or separately into the reaction zone near the point of entrance of the reactants, and the next portion of catalyst, generally smaller, is added at a point at which the first portion is mostly deactivated; at any rate, the relationship of the yamount of catalyst thus introduced to the extent of deactivation of previously introduced catalyst is such that the ratio of total catalyst activity to volume of reactants at that point is less than at the earlier point of catalyst introduction, the difference being generally inversely proportional to temperature. It would not be at all desirable to introduce catalyst increments of equal activity at equal points while the temperature is rising. As the temperature increases in the direction of flow of reactants, the catalyst activity decreases so as to avoid a, constantly increasing conversion rate as would normally be encountered.

The above discussion is directed towards processes carried out under adiabatic, or at least partially adiabatic conditions in which the heat of reaction causes a temperature gradient to exist along the direction of flow of reactants. A combination of indirect heat exchange to partially overcome heat of reaction, with the controlled introduction of catalyst as described above, may be used for exothermic or endothermic reactions.

In case it is desired to maintain substantially isothermal conditions in endothermic or exothermic reactions by means of indirect heat exchange or other methods, this invention may be utilized to obtain a more satisfactory control of reaction and to simplify the temperature control. When reactants are passed through a stationary bed of catalyst, or contacted with a single portion of mobile catalyst, there is a tendency for the reaction to proceed too rapidly at rst, with consequent overheating or cooling, as the case may be, at the rst point of contact between reactants and catalyst and too rapid catalyst deactivation at that point. However, by adding catalyst to the reaction zone in controlled increments in accordance with my invention, the extent of reaction and temperature may be maintained under strict control since reactants are contacted with a limited portion of catalyst, and are not contacted with an additional portion until the temperature is brought back to the desired value. The catalyst is not added haphazardly, but the addition is carefully correlated with the amount of heat produced or consumed by the reaction and with the amount removed or introduced, so as to avoid localized spots of overheating or excessive cooling. Catalyst and reactants may flow countercurrently or concurrently, depending upon the type of reaction, catalyst, etc., the proper modiiications being readily chosen in view of the detailed disclosures offered herein.

One advantageous aspect of the present invention is the controlled use of the catalyst itself as a heat transfer or carrying medium in endothermic or exothermic reactions, the temperature and quantity of the catalyst introduced at each point being so correlated with the other factors herein discussed as to supply endothermic heat of reaction or take up exothermic heat of reaction. This is particularly desirable where temperatures can not be allowed to vary too greatly, and isothermal conditions, or at least -conditions which approach isothermal, are accordingly preferred. Claims in the present application are particularly directed toward this subject matter.

Other operating problems frequently encountered in catalytic reactions involve catalyst deactivation and means for avoiding same or for reactivating catalyst, the activity of which has dropped to an uneconomic level. Mobile catalysts are generally subjected to reactivation treatment either after each passage through a reaction zone, or a portion only may be treated each time to keep the overall activity at the desired level. One of the advantages of mobile catalysts over stationary cataysts is that control of regeneration is thus obtained in a fairly simple manner. However, only the overall? activity is thus affected, the actual activity at any particular point in the reaction zone being dependent upon conditions therein which are not readily changed with respect to deactivation of catalyst which is occurring. For example, many catalysts will be subjected to a rather extensive deactivation in a relatively small rst portion of the reaction zone, due to temperature conditions, poisons, etc., with deactivation in subsequent portions of the reaction zone continuing at a much slower rate. In such a case, it will be seen that while the average or overall activity may be regulated, the uneven loss in activity causes an ineiiicient operation.

My invention provides a means for controlling the activity of mobile catalysts at any point in a reaction zone. This may readily be accomplished by controlling the quantity and/or activity of catalyst introduced at the diierent points. Thus in certain cases, partially or completely deactivated catalyst may be admixed in varying proportions with fresh or reactivated catalyst to give the desired activity for introduction at any particular point. In fact, in some cases more than one different type of catalyst may be used for introduction at different points into a single reaction zone to give controlled activity, which may be either maintained constant or varied from point to point to meet the needs of the particular reaction being catalyzed. Examples given herein will serve to point out more clearly a few of the many ways in which controlled variation or constant activity of catalyst is obtained and correlated with other reaction conditions through use of this invention.

Another method by which my invention makes possible a more eiective use of catalyst is by controlling the quantity and/or activity of mobile catalyst in a reaction zone in relation to the concentration of reactants existing at various points in the zone. The change in concentration of reactants in a reaction zone depends upon the extent of conversion occurring. If, as in many cases, a substantially complete conversion of reactants to products is desired by the time the reaction mixture leaves the reaction zone, it will be seen that the concentration of at least one reactant must approach zero at the reaction zone exit. In many other reactions, however, an equilibrium may exist which prevents, or economic considerations may make undesirable, a complete conversion. The extent of conversion may vary greatly with the type of reaction being catalyzed, one process involving say a one per cent conversion per pass while another may accomplish forty, sixty, or more per cent conversion in one pass. Ordinarily in case the percentage conversion is low, the loss in concentration of reactants as the reaction proceeds does not greatly affect the reaction rate. However, in the case of higher conversions ranging on up to per cent, the lowered concentrations of reactants existing in the latter parts of the reaction zone may greatly decrease the reaction rate, even though expedients such as using a large excess of one reactant 0r the like are resorted to. By controlling the multipoint introduction of catalyst in accordance with the decrease in reactant concentration I may partially or completely compensate therefor, and avoid too great or any decrease in reaction rate by providing more catalyst activity at the points of lower concentration. The dilution effect of the catalyst is also to be considered. Again, the catalyst may pass either concurrently or countercurrently to the reactant depending upon the various factors involved for any particular reaction.

It is to be understood that the various methods of utilizing the present invention, that is, for example, by controlling the introduction of catalyst to compensate for changes in temperature, catalyst activity, reactant concentration, etc., may be used either alone or in various combinations, one with the other, as will be well understood by one skilled in the art in view of the full and complete disclosure given herein. Obviously the choice of one or a combination of methods of operating will have to be made with due consideration for the reactions being catalyzed, the type of catalyst most suitable, the extent of reaction, the thermal changes involved, the necessities and possibilities of applying reactivation processes to the catalyst, etc. Various modifications such as introducing diluents, refrigerents, heat carriers, reactants. and the like, lmultipoint along with or separately from the multipoint-injected.`

catalyst, may be used as found advantageous for any particular process.

A numerical treatment may be used at this point in order to bring out more clearly the'hereinbefore discussed principles upon which the inventionis based. A number of assumptions will be made to eliminate variables and simplify the presentation. A simple example would be an endothermic conversion involving heterogeneous catalysis, for example the conversion of an organic fluid using a solid contact catalyst in nely divided form. The data below will show how the invention is utilized to maintain a constant reaction rate by overcoming the effects of decreasing temperature, decreasing concentration Aof reactants, and any deactivation of the catalyst, which would, if the invention were not used but the same total conversion were obtained, cause the reaction rate to drop to a value in the last part of the reaction zone equal to only one-sixth that at the rst part of the reaction zone. Assume no change in volume of reactants upon reaction, and assume that doubling the number of particles of catalyst will cause twice as much reaction to occur in a given time due to the doubled area of catalytic contact surface oered the reactants. Let a cylindrical reaction zone through which reactants and catalyst flow concurrently at the same ratebe considered as divided into six cylindrical increments of equal volume referred to hereinafter as unit volumes. Let 0.5 unit volume of reactants enter one end of the reaction zone per minute, and a total of 0.5 unit volume of catalyst enter the zone per minute in equal increments of 0.083 volume at each of six equally spaced points; that is, 0.083 volume of catalyst is introduced into each of the six aforementioned incremental unit volumes of the catalyst zone. In the first unit volume of the reaction zone, the ratio of volume of catalyst to volume of reactants 1s 10 in the sixth and last unit volume of the reaction zone the ratio is Thus the ratio of catalyst to reactants at the outlet is 1.0 m-ll times that in the inlet, and accordingly, the effect on the reaction rate would be to increase the rate 11 times. Considering now the contact time, it will be seen on following 0.5 volume of reactants through the catalyst zone that it requires minuites to traverse the first unit volume of the zone and v,minute to traverse the ,last unit volume of the zone. Thus itis seen that the contact time of reactants withtheparticular amount of catalyst present inthe various zones is less in the later increments of the reaction zone than in the earlier increments, and` therefore the tendency is for the extent of conversion to decrease. The eifect ofv contact'time alone on extent of conversion is equal to that is, the lconversion-would be approximately halved. Takingthe two effects. of contact time and ratio of catalyst to reactants, the overall tendency toward change inconversion would be approximately expressed as f reactants, etc., to the extent that any of such changes in conditiuns, or the effect of all combined, tend to cause a six-fold decrease in reaction rate. In similarcases in vwhich the depressing influences on the reaction rate are greater or less than six fold, the rate would be held constant by a corresponding increased or decreased overall ratio of catalyst toreactants, or by a controlled change in the .activity of.- catalyst introduced at succeeding points, etc., the exact conditions -being calculated in a manner similar Ato that shown above. Application of this type of procedure to a specic endothermal reaction will be described in more detail hereinbelow with ref erence to Figure 1. In order to explain the invention more fully, the following examples and appended drawings are provided to illustrate specific embodiments of the process, but no limitations are thereby implied, inasmuch as the invention may be utilized in numerous other manners by following the teachings of this disclosure. Figure 1 shows in diagrammatic form an arrangement of equipment for carrying out the catalytic cracking of petroleum oils, an endother-v mic reaction, using a nely divided solid catalyst suspended in vaporous reactants and thus flowing concurrently therewith, commonly termed a fluid catalyst process.

Figure 2 shows diagrammatically apparatus for polymerizating butenes, an exothermic reaction, in which a gaseous catalyst immiscible with the liquid reaction mixture is passed countercurrently to the reactants.

Figure 3 is a diagrammatic drawing of apparatus used for the vapor phase reduction of nitrobenzene with gaseous hydrogen, an exothermic reaction, wherein a metal catalyst supported on a solid granular carrier material is passed concurrently with, but at a different rate than, the reactants.

Figure 4 illustrates diagrammatically one form of apparatus and ow of materials therethrough in which hydrocarbons are cracked at substantially constant temperature, using a moving bed of solid catalyst which is introduced hot into the reaction zone at a plurality of points for downward flow concurrently with reactants.

In Figure 1, the reactant, for example gas-oil derived by straight-run distillation of crude petroleum, passes from line I into blower II, and

thence through line I2 into heater I3 wherein it is raised to a suitable temperature such as 900 F. for the initiation of the reaction upon contact with the catalyst. From heater I3 the heated reactants are sent through line I4 into the reaction chamber I5. This reaction chamber may take the form of an elongated tube, as shown diagrammatically in Figure 1. Various types of reaction chambers suitable for use with powdered catalysts are known in the art. A very nely divided solid catalyst is injected into reaction chamber I5 at spaced points along the path of flow of reactants through line I6, Il, I8, and I9. Obviously, although only four lines are shown, the number of such lines may be varied at will to obtain suitable operating conditions compatible with economy of equipment. The catalyst may be of the ntaural clay type such as fullers earth, bentonite, etc., preferably activated in known manner, or of the synthetic type such as silicaalumina or other effective catalysts known to the art. The method of introducing the finely divided catalyst into the reaction zone may include such operations as suspension in liquid or gaseous reactants or diluents.

The catalyst may enter lines I6, Il, I8, and I9 from two sources. The rst source is conduit which carries recycled catalyst which has been partially deactivated by previous use in the process. The second source is conduit 2I which carries regenerated catalyst from catalyst regeneration zone 22. Carbonaceous deposits are removed from the catalyst in zone 22 by burning in an oxygen-containing gas. The quantity of catalyst from each source injected at each point is regulated by suitable means so that all of the catalyst entering through line I6 is the partly deactivated catalyst from conduit 28; most of that entering through line I1 is of the same type, but has admixed with it by means of line 23 a small portion of freshly regenerated catalyst from conduit 2|; that entering through line I8 has a larger proportion of reactivated catalyst, which reaches line I8 through line 24; and that entering at the last point through line I9 is composed entirely of regenerated catalyst from conduit 2I.

The mixture of products, excess reactants if any, and catalyst passes from reaction zone I5 through conduit 25 into a catalyst separation zone 26, which may be a cyclone separator, electrical precipitator, or any other suitable means for accomplishing the separation of finely divided catalyst from the hot vapors. Catalyst passes from zone 26 into conduit 21 and a portion is taken from conduit 2l through conduit 28 to the catalyst regeneration zone 22. Vapors leave the catalyst separating zone 26 through line 29, and may be condensed and fractionated to separate out the desired cracked gasoline product, with unreacted gas-oil being recycled to the reaction chamber. If desired, various other modifications of such a cracking process which are known to the art, for example recycle of very small amounts of hydrogen, etc., may be used.

The cracking of petroleum oils is an endothermic process, and, as heretofore explained, under ordinary methods of operation a substantial temperature drop occurs which causes a decrease in reaction rate as the reactants proceed through the cracking zone. However, by controlling the relative volumes of partially deactivated and of activated catalyst and also the total volumes of the catalyst introduced into the reaction zone as just described, in conformity with the principles heretofore discussed in detail, the total catalytic activity at each succeeding point in the cracking zone in the direction of ow of reactants is greater than the activity at the preceding points, the increase in activity being such that the normal decrease in reaction rate accompanying dropping temperatures and catalyst deactivation is partially or completely obviated. This increase in total catalyst activity is obtained by the increasing volume of catalyst due to its multipoint introduction, and the increasing activity of the catalyst introduced, due to the use of relatively greater proportions of freshly reactivated catalyst in the increments introduced along the path of flow of reactants. Of course, the actual quantities of catalyst introduced at the various points will depend upon the catalyst being used, its rate of deactivation under the given reaction conditions, rate of flow of reactants and catalyst, extent of reactivation effected in the catalyst regeneration zone, the characteristics of the gasoil being cracked, temperature and pressure conditions in the cracking zone, extent of indirect heat exchange occurring between the cracking furnace and any outside sources of heat or cooler surroundings, etc. However, the general principles set out in this disclosure will readily enable one skilled in the art to correlate these various factors for any particular application to obtain the advantages of the invention. Although in the drawing the first point of catalyst introduction into the reaction zone is shown past the reactant inlet, this rst point may also be positioned at or just before the inlet so that the iirst increment of catalyst enters along with the reactants.

It will be noted that in the cracking process as shown in Figure 1, several of the aspects of my invention which were described before in some detail may be involved. For example, the endothermic nature of the reaction will, unless sufficient heat exchange is provided, cause the temperature to drop. The multipoint introduction of catalyst is so controlled as to counterbalance this effect in order to maintain desired reaction velocities. The catalyst during its travel through the cracking zone becomes at least partially deactivated, thus tending to slow the reaction even at constant temperatures. Additional catalyst, including regenerated catalyst, is

introduced in such quantities as to compensate for the deactivation occurring in the cracking zone. Another factor tending to decrease reaction rates is the decrease in concentration of reactants which occurs as the reaction proceeds. Since in a gas-oil cracking process of the type described, only partial conversion, say from to 40 per cent, is permitted to occur in one pass, the decrease in reactant concentration does not influence the course of reaction so much as in the case of reactions giving complete conversion in a single pass. However, any elect of this kind is readily overcome by the controlled addition of catalyst at the different points along the cracking zone.

Thus it is seen that in a typical process, gaso il cracking, control of catalyst addition may be related to several variables. On the other hand, well known expedients might in some cases be utilized to control certain of these variables. For example, sufficient heat may be introduced into the cracking zone by various means as to maintain a substantially constant temperature, although this is difficult to accomplish in actual practice, at least by indirect means. In such a case, catalyst addition at points would be controlled to make up for the combined effects of loss in catalyst activity and change in reactant concentration. A specific example of this is given below in conjunction with Figure 4. On the other hand, reaction conditions may be maintained which are so mild that the amount of catalyst deactivation occurring in a single pass will be very slight, so that the principal purpose of introducing the catalyst at points will be to compensate for decreasing temperatures and/or concentration of reactants in order to maintain a substantially constant reactionl rate. In Figure 2, an elongated reaction chamber 40 is provided, the interior of which may be lled with packing material for promoting intimate contact between gases and liquids. Fed to the system through line 4I is a gaseous hydrocarbon mixture containing a substantial proportion of butenes, preferably isobutylene although normal butenes may also be present. This gas is compressed in compressor 42 and then passes via line 43 to heat exchanger 44 where it is cooled by indirect exchange with effluents from the reaction chamber. cooled hydrocarbons pass via line 45 into the top of reaction chamber 40, wherein they are subjected to the polymerizing action of boron triiluoride (BF3) as hereinafter described. Refrigeration means 46 is interposed in line 45, and serves to cool the reactant feed to the desired reaction temperature, in this case -30 C. The" hydrocarbons making up the feed are in liquid phase at this temperature, and the reaction chamber is operated at substantially atmospheric pressure.

Ordinarily a C4 fraction is used which contains substantial amounts of butanes, which serve as a diluent and as a solvent for the high molecular weight polymers formed in the reaction. vIf such butanes are not available admixedwith the butenes, they may be supplied, or pentane or other suitable saturated hydrocarbon solvent may be used. The liquid butenes and accompanying hydrocarbons flow downwardly in chamber 40 countercurrent to gaseous BFa and gaseous propane, and substantially complete polymerization of the butenes occurs to vform polymers of a molecular weight suitable for use as lubricating oils, additives to oils, etc.

From the heat exchanger the The boron fluoride catalyst passes from conduit 41 into reaction chamber 40 at a plurality. of points by means of valved lines 48A- 48G inclusive. Also introduced into chamber 4ll-at the same points is liquefied propane from conduit 49 via valved lines SUA-50G inclusive. This liquid propane acts as a coolant, diluent, and disperant for the BFa, as will be explained in more detail below. Ordinarily a catalyst activator such as hydrogen fluoride, or other materials which will cause the production of hydrogen halides in the reaction zone, is introduced in small amount along with the boron fluoride or otherwise. Furtherg more, metallic nickel or other metals are occasionally used in the reaction zone to help catalyze or promote the reaction.

The butenes upon first entering chamber 40 andl beginning their downward flow therethrough come into contact with a gas phase which .comprises pro-pane and BFa. The volume of the gas phase is greater at this point than at any other point in the chamber. Polymerization is initiated by the catalytic action of the boron fluoride. This polymerization reaction is highly exo.- thermic, and the temperature must be held under very careful control, particularly since the type of product obtained may change greatly with a relatively small change in temperature; thatis'-, the product formed at 30 C. may have an average molecular-weight several times that of the product formed at 0 C. vFor this reason; it is preferred to carry out the reaction as nearl isothermally as possible.

The amount of boron fluoride introduced will ordinarily vary from point to point, being smallest at the top point (conduit 48A) and greatest at the bottom point (conduit 48G). By this multipoint addition of the catalyst, a much more eilicient reaction control is realized, since the reactants do not contact the total'amount of catalyst at once. The catalyst contacted at the first point comprises not only that introduced through conduit 48A, but also any bubbling up from the lower part of the reaction chamber. Just enough is introduced through line 48A to furnish suicient fresh catalyst to initiate the reaction to the desired extent. It will be seen that the downward-flowing reaction mixture con'- tinuously contacts upwardly flowing catalyst. Due to the formation of complexes lbetween boron uoride and olefins, a substantial part of the catalyst combines with reactants and is carried down as complex. Such complexes have only a limited amount of catalytic activity, if at all. Thus, if all the catalyst were introduced atl the bottom, it would be continuously reacting'with olens as it rose through the chamber, and th'e upper part of the chamber would be deficient in catalyst. In order to ensure that some catalyst reaches the top of the chamber, an otherwis'e unnecessary excess would have to be introduced at the bottom. Much better results are obtairied by the multi-point addition, by which each increment added to the gas phase flowing upward through thereaction chamber can be controlled in amount to give just the desired concentration of catalyst at the given point. It is preferable that the amount of catalyst be relatively small at the top of the chamber where the reaction starts, since the major part of the reaction and thus heat evolution generally occurs in the upper half of the chamber where the greatest concentration of monomers is found.

The introduction of controlled amounts of cold liquid propane at points along with the catalyst gives effective control of temperature throughout chamber 40. The propane vaporizes immediately upon entering the chamber, and in so doing absorbs the heat of reaction. Of course, additional indirect heat exchange may be provided for chamber 40 to assist in removing the heat of reaction if desired, particularly in order to avoid having too large an amount of gaseous propane passing through the reactor. A convenient way to do this is to pass chilled liquid propane through Vcoils in chamber 40 in indirect heat exchange with the reactants, and then to pass the desired amount of the propane into conduit 49 for direct introduction through conduits 50A, 50B, etc.

Since the amount of BFa used is only a small percentage of the hydrocarbons charged, say from 5 to 5.0 mol per cent, the propane gas is very eiective in promoting a more thorough dispersal of the catalyst throughout the reaction zone. It also serves as a diluent both for the liquid re actants and for the gaseous BFA. For this reason, larger amounts of BFa may be passed through reaction chamber 40 thus admixed with propane than would be suitable in the absence of the added gas. This excess BFa is recovered and recycled. The amount of liquid propane added through the lower conduits, for example, 50G to 50F, is less than that added through the upper conduits such as 50A and 50B. This is because more heat of reaction is developed at the top of chamber 40 than at the bottom, and more evaporation of propane is needed at the top to maintain the desired low temperature.

Flow rate of reactants through chamber 40 is preferably such that substantially no unpolymerized butenes are present in the eluents and the polymers in the eiiuents are predominately of high molecular weight, for example over 2000. The character of the polymers can be controlled to a certain extent by controlling the reaction time and thus the extent of conversion, although a change in operating temperature will generally have more influence on the final product. A short conversion time will ordinarily produce some of the high molecular weight polymers, with a larger percentage of intermediate polymers which may be used for different purposes or which may be recycled to reaction chamber 40. The volume of propane gas passed through reaction chamber 40 will generally be several times the volume of liquid reactants and solvent passed through the chamber in a given time.

Propane gas and boron fluoride gas leaving the top of chamber 40 via vline 5| are compressed in compressor 52, chilled, by partial evaporation in known manner, if desired, in refrigeration means 53 to condense liquid propane, and then passed to accumulator 54. Cold gaseous boron fluoride leaves the top of accumulator 54 through line 41 for re-use in the process, while cold liquid propane leaves the bottom of accumulator 54 by line 49 to be introduced into chamber 40 as described above. Of course, the gas phase from accumulator 54 contains some propane, and the liquid phase contains some boron fluoride in solution. Since 'butenes are appreciably volatile at the temperature of operation of chamber 40, the gas leavingthat chamber via line has some butenes in it, and these butenes tend to undergo some polymerization in line 5| and compressor 52. For this reason, it is desirable that the leng-th of line 5| between chamber 50 and compressor 52 be short, and that the line 5| and compressor -be flushed periodically with a solvent for the polymers such as liquid butane. Not much trouble is experienced from compressor 52 on, since liquid propane is present which acts as solvent. The amount of polymer formed is small compared to the amount of butenes passing through this part of the system, most of the butenes returning unchanged nto reaction chamber 40 along with the propane. A very satisfactory way to obviate any difficulty in this regard is to wash the gas in line 5| with sufficient liquid butane or pentane to remove practically all of the butene. The liquid may then flow directly into chamber 4U. This modification is not shown in the drawing for the sake of simplicity.

Liquid products leave the bottom of reaction chamber 40 through line 55 and pass through heat exchanger 44 to be warmed to a higher temperature and to cool the incoming butenes. From exchanger 44 the products pass via line 56 to separator 51 wherein dissolved and/or entrained boron fluoride and propane gas are evolved, which pass via line 58 to line 5| for recovery and re-use. Liquid products pass from separator 5l via line 59 to boron fluoride and solvent recovery means which are indicated diagrammatically at 60. The solvent, which ordinarily is butane, is recovered by evaporation and leaves the system through line 6|. Part or all of the solvent may of course be recycled to line 4| or elsewhere if desired. Boron fluoride is recovered from its complexes by heating or other means, and is returned to the system by lines 62, 58, and 5|. Ordinarily heating the product to C. or higher will serve to release at least part of the boron uoride from the hydrocarbons. Polymer is removed from the system at 63. Any make-up BFa and/or propane required may be supplied through line 64.

The above-described process exemplifies an adaptation of my inventionto a highly exothermic reaction wherein the temperature is maintained constant. The multipoint addition of catalyst is controlled with respect to two principal variables. One is the loss of catalyst by complex formation. Catalyst is added at points to maintain the desired amount of active catalyst. The other is change in concentration of reactants. The smallest concentration of catalyst is maintained at the point of greatest concentration of butenes, while the greatest concentration of catalyst is at the outlet where reaction is being completed with practically no butenes remaining. It is to be noted that due to the diluent effect of the gaseous propane, the actual quantity of catalyst may under certain conditions be greater at the top point than at the bottom point, but the ratio of catalyst activity to reactants decreases from bottom to top, the diluted catalyst having less effect than the undiluted catalyst. The catalyst activity thus changes in relation to the extent of reaction, to compensate at least in part for the tendency toward decreased reaction rate.

An import/ant aspect of the polymerization process as described is the fact that, while actual cooling is accomplished by the propane, temperature control is effected to a large extent by the multipoint addition of the catalyst. This is because the rate of addition of catalyst at each point is so controlled and correlated with the other factors that catalyst activity at the point of greatest tendency toward heat evolution, that is the butene inlet, is smaller than at any other point, and the catalyst activity is increased as the tendency toward heat evolution decreases. The entire process may be contrasted with the prior art methods wherein the boron fluoride is 17 added all at one' point with consequent violent reaction at that point with little or no reaction at other points or wherein ineflicient batch methods are employed with vigorous stirring, gradual addition of catalyst and/or reactants is resorted to, and the reaction time is unduly extended because of the inherent limitations of that method of operating.

In Figure 3, the reaction chamber l is preferably provided with means (not shown) for removing at least most of the heat of reaction by indirect heat exchange. A certain amount of heat is also lost to the atmosphere,- but in order to avoid uneven cooling the entire chamber is ordinarily provided with some insulation. Heated vaporized nitrobenzene from line 1 I and hydrogen from line 'I2 join in line 13, and flow into reaction chamber for downward flow therethrough. The hydrogen may be admixed with substantial amounts of carbon monoxide, or with inert gases such as methane or nitrogen. In fact, in carrying out the reduction of nitrobenzene in accordance with the present invention, I prefer to have some inert gas with the hydrogen. The ratio of hydrogen to nitrobenzene must be held within relatively narrow limits to obtain the highest yield of aniline, since a ratio considerably higher or lower than the stoichiometrical amount gives rise to reduction products other than aniline. It is best to have somewhat more than the theoretical ratio of hydrogen to nitrobenzene, but not too much more, in order tojensure completion of the reaction, and some inert gas is preferably used in admixture with the hydrogen.

A suitable supported hydrogenation catalyst in granular form is caused to pass through conduit 14 into manifold 15. Branching off from manifold 15 are branches 16A-IBF inclusive through which the catalyst is introduced into the reaction chamber 'I0 at. spaced points along the path of ow of reactants. The quantity of catalyst introduced through each branch 16A, etc., may be controlled by any suitable means. It will be appreciated that due consideration must be given to the fact that chamber 10 is operated under pressure. The lines, 16A to ISF inclusive, are shown equally spaced; however, the lines may be more or less in number, and evenly or unevenly spaced, in accordance with the capacity of the system, convenience of fabrication, operating conditions, rate of catalyst introduction at the various points, and economy of equipment. A series ofv baiiles 11 is provided in chamber 10 to keep the catalyst particles dispersed and in good contact with reactants as the catalyst falls to the bottom of chamber 10. These baiiies preferably have only av slight inclination fromthe Yhorizontal so that catalyst is more or less pushed olf of one bale down to the next by incoming cat/alyst.

In the hydrogenation of nitrobenzene by prior methods, the reaction mixture is passed through aV stationary bed of catalyst. Since the con-centration of reactants is greatest in the iirst portions of the catalyst bed, the major part of the reaction occurs before the bed is halfway traversed. This means that the amount of heat liberated in the upper parts of the catalyst charnber is greater than in the lower parts, and thus the load on heat exchange coils or the like with which the chamber may be provided is greatest at the top and least at the bottom. Thus the heat exchange means must either be oversized at points or is overloaded. In practical operation, the heat of reaction cannot be satisfactorily'removed, and a serious temperature rise occurs.

This is very undesirable, since the optimum yield of aniline, when using any given catalyst, is obtained only in a relatively narrow temperature range. Sintering of catalyst is also likely to occur on the most active catalytic points where to a hundred or so degrees centigrade higher than the mean temperature of the reactants and catalyst near those points. A further disadvantage lies in the fa'ct that the temperature rise serves to increase the already excessive reaction rate still more.

By means of my invention the catalyst addition is controlled in accordance with the rate vof reaction or rate of evolution of heat, so that substantially equal, or at least regularly varying quantities of heat are evolved and removed along ecual increments of the length of reaction chamber 10. Thus. in the first part of reaction chamber 10, a relatively small amount of catalyst is introduced through branch 16A. Since lr-he highest concentrations of nitrobenzene and of hydrogen are found in this portion of the reaction zone a small amount of catalyst is sufcient to promote considerable reaction. As the reaction rate tends to lessen due to the diluent eects of the aniline formed, or stated another way, due to the lowered concentrations of nitrobenzene and hydrogen, additional catalyst enters the reaction zone through 16B, and th reaction rate tends-to increase against. Thus, the quantity of active catalyst surface present at various points in reaction chamber 10'is maintained suiliciently, as the reactants flow therethrough, so as to give a completely reduced prod- The amount of catalyst in Y' the parts of chamber 10 is small at the inlet uct in the effluents.

ture may be maintained substantially constant.

due to the fact that the amount of heat liberated is notJ excessive at any point, or a gradual temperature gradient may be allowed to exist, an increase of say 50 C. from the inlet to the outlet being permissible without undesirable effects. It is to be noted however, that in using my invention, such a temperature gradient is regular, and is obtained gradually as the reactants'fiow through the apparatus, rather than being obtained all at once as by other methods, in 'which case a peak temperature may even occur, with a subsequent falling off in the latter stages where very little reaction is occurring.

'A certain amount of catalyst deactivation will occur which tends'to lessen the reaction rate, and

this is also compensated for by the freshV catalyst troduced at the various pointswill be determined as described above with referenceto control of rate of reaction, while the total rate of 'catalyst @QW in tQ and thence out of chamber 'l0 will generally be chosen with respect to the type of reactivation treatment to which the catalyst is subjected outside the chamber. It is usually preferable to reactivate the catalyst before it has losttoo much of its activity, since considerably higher temperatures frequently must be used in the reaction zone with a less active catalyst. Thus it is seen that a continuous ow of catalyst is maintained through chamber so that the catalyst as removed from the bottom thereof is usually still fairly active. The rate of ow of gaseous reactants through the catalyst chamber 10 will be many times greater, on a volume basis, than the rate of iiow of catalyst therethrough.

The total effluent from reaction chamber 10 passes out through conduit 18 and then to catalyst separator 19 where the catalyst separates from the gases by gravity. This catalyst is removed through conduit 80 containing suitable conveying means such as screw 8|. From 80 the catalyst passes through conduit 82 to conduit 14 for re-use in the process. A portion of the catalyst stream may be continuously by-passed through a regeneration zone indicated diagrammatically at 83 to maintain the total catalyst stream at the desired activity. The regeneration in zone 83 comprises conventional chemical treatments to remove accumulated impurities and to restore the catalyst to substantially its original conditions. The entire stream of catalyst, rather than a portion, may be passed through regeneration zone 83 if desired.

The gases in catalyst separator 19 comprise aniline produced in the process, any traces of unreduced nitrobenzene, steam formed as a byproduct, any excess hydrogen, and any inert gas introduced along with the hydrogen. This gas phase is passed via line 84 through cooler 85 and into product separator 86, wherein a liquid waterrich phase, a liquid aniline-rich phase, and a gaseous phase separate out. The gas is recycled via, line 81 to line 12 for re-use of the hydrogen in the process. In order to prevent inert gases from pyramiding in the system, a portion of the gas is allowed to leave line 81 through valved branch 88. The aniline is removed from separator 86 through line 89 and passed to suitable apparatus for removing dissolved water and any other impurities. Water is removed from separator 86 through line 90,'and passed to a system for recovering dissolved aniline therefrom. One

very effective method of accomplishing this is to extract the aniline from the water with nitrobenzene, the extract then being led to the reaction zone for reduction of the nitrobenzene.

Suitable catalysts for the reduction of nitrobenzene according to the system just described may comprise metals such as gold, silver, nickel, copper, or tin, either alone or in admixture, and preferably supported on granular carriers such as pumice, porcelain, alumina, etc. It is necessary that the catalyst composition have: sufficient mechanical strength for withstanding the effects of continuously moving through the equipment. A preferred catalyst comprises supported tin prepared from the precipitated hydroxide or carbonate. With such a catalyst, an operating temperature in reaction chamber 10 in the range of about 275 C. to 375 C. is suitable.

Referring now in detail to Figure 4, approxi-- mately 350-400 barrels per hour of gas oil, which may be a West Texas virgin gas oil boiling in the range of from 400800 F. and having a gravity of 33-38 API, is introduced into the system through une lul, then heated in a are@ beater |02 or other suitable means to a temperature such as S-900 F. and passed through line |03 to the cracking. reactor |04. The pressure employed in the reactor may be atmospheric or thereabouts, for example, in the range 0-15 pounds per square inch gauge. The desired average temperature in the reactor may be in the range 86C-870 F. The catalyst may be a natural or acid-treated bentonitic clay or a synthetic gel of silica and alumina, in the form of pellets or beads. In reactor |04 the hydrocarbon reactants are mixed with and ow concurrently with the catalyst, which is introduced multipointwise as previously described` through lines |05, |06, |01 and |08. In this embodiment the reactor is maintained full of catalyst, which moves slowly downward in the form of a moving bed, and at a slower rate than the vapors. The catalyst introduced at the uppermost point through line |05 is comprised predominantly or entirely of unregenerated though still active catalyst, which is recycled from the reactor outlet through line |09, separator ||0, line III, heater ||2 and line 3, and which amounts to approximately 60-70 tons per hour. This initially introduced spen catalyst together with the hydrocarbons charged then continue downwardly in the reactor where additional catalyst of preferably higher average activity is vintroduced through line |06. Approximately -100 tons per hour comprised of 40-50 weight per cent spent catalyst are injected at this point. Through line |01, there is injected approximately 35-45 tons per hour of catalyst of still higher average activity with this catalyst stream comprising 20-30 weight per cent spent catalyst. Near the lower end of reactor |04, the catalyst injected through line |08 is preferably comprised substantially of regenerated catalyst and is 15-20 tons per hour in quantity. It is to be understood-that any suitable number of catalyst injection points may be used to introduce catalyst to the reactor so long as there are several such points, and four points are indicated for the purpose of illustration. The catalyst together with cracked products and unreacted hydrocarbons leave reactor |04 through line |09 and pass to separation zone |0 where the hydrocarbon vapors are separated from the catalyst and passed by means of line ||4 to further known separation and fractionation steps for the recovery of desired products. The catalyst separation zone ||0 is shown diagrammatically and is not to be limited to any specific means of separation.

The spent or unregenerated catalyst passes through line and valve ||5 to regenerator |28 where the carbonaceous deposit on the catalyst is removed by a series of burning operations using an oxygen-containing gas such as air to support combustion. The regenerated catalyst leaves the regenerator at a temperature of 940- 975 F. through line |1 and is returned to the reactor by means of valves I8, ||9 and |20 and lines |06, |01 and |08. A portion of the spent catalyst is passed through valve ||6 and line |2| to heater ||2 where the temperature of this catalyst stream is raised to a desired level, such as S90-910 F. The catalyst may be heated in heater ||2 by any one of several means, either direct or indirect, for example as by superheated steam, indirect exchange with hot regenerated catalyst, or as shown here by indirect heat exchange with the flue gases from the regenerator. When such flue gases are substantially oxygen-free, the heat @Xchange may be l.by direct Contact of gases with 2l catalyst. The heated spent catalyst is then passed to the reactor through line ||3, lines |22, |23 and |24, valves |25, |26 and |21, and lines |05, |06 and |01 as previously described. It is to be appreciated that the relative proportions of spent catalyst and of regenerated catalyst injected into the reactor may be varied widely with the portions stated serving simply to illustrate one manner of operation of my invention.

In the regenerator, air or other oxygen-containing gas may be introduced multipointwise through line |29, valves |30, |3|, |32, and |33, and lines |34, |35, |36, and |31 to burn the carbonaceous deposit from the spent catalyst. The flue gases resulting from the combustion are removed through lines |38, |39, |40, and |4|, valves |42, |43, |44 and |45 and line |46 and passed to heater ||2, being then removed from the system through line |41. The temperature of the ue gases may be in the range S40-975 F. The introduction of the oxygen-containing gas and subsequent removal of the ue gases need not be made in a multipontwise manner and can be done by any one of several known methods.

There are several modifications and variations of my invention that may be practiced. Forexample, a portion of the spent catalyst may be mixed with the charge in line |03 prior to its introduction into reactor |04. Another desirable modification is the introduction of the relatively deactivated catalyst into the regeneration zone multipoint, rather than at one point as shown through line and valve H5. By use of suitable means not shown, the catalyst can be injected at a plurality of points along the length of the regenerator with proper means being used for introducing oxygen-containing gas and for removing the resultant ue gases. It is thus possible under suitable conditions to obtain better temperature control and more uniform burning in the regeneration zone. In the operation shown, in which a downwardly moving bed of catalyst is used in the regenerator, the oxygen-containing regeneration gas may advantageously be introduced at the bottom for flow counter-current to catalyst which has been introduced at several points along the reactor. and additional cooling and/or diluent gases with or without oxygen, may be introduced at the same or diierent points for upward ow, the total gases being removed from the top of the reactivation zone.

Various modes of operating have been disclosed herein, along with the broad concepts involved, so that one skilled in the art may, by suitable simple modifications, apply the principles of my invention to conform to the economic and practical considerations which will vary somewhat with each particular material treated. By following the teachings of my invention, the contacting of catalysts with reactants may be so exactly correlated with reaction conditions as to give a well regulated operation not heretofore taught. While I have disclosed certain specific processes, with particular reference to petroleum conversions, I do not wish to be limited to the exact modifications described, but only by the rppended claims.

I claim:

l. A process yfor the catalytic cracking of petroleum oil into lower boiling products which comprises passing vapors of said oil through an elongated reaction zone at cracking conditions of temperature and pressure such that normally there would be a temperature decrease in the direction of flow due to the endothermic cracking reaction, introducing powdered cracking catalyst from two sources as hereinafter described into said reaction zone at a plurality of points spaced in the direction of flow for suspension in said vapors, separating said lower-boiling products from the eilluents of said reaction zone, separating substantially all of the catalyst so introduced from the eiuents of said reaction zone, the thus-separated catalyst still retaining some activity, reactivating only a portion of said separated catalyst by burning carbonaceous matter therefrom in an oxygen-containing gas at a temperature higher than said cracking temperature to form a portion of hot reactivated catalyst and a hot oxygen-free gas, separating said hot oxygen-free gas and contacting same directly with the remainder of said separated catalyst which has not been reactivated to heat the latter to a temperature above the cracking temperature, recycling the thus-heated remainder of said separated catalyst without reactivation to a plurality of said points `including the rst and excluding the last of said points in the direction of flow, the unreactivated catalyst introduced to said rst point being the sole catalyst introduced thereto and a, diminishing quantity of unreactivated catalyst being introduced at each succeeding point in the direction of ow, introducing the hot reactivated portion of said catalyst into the reaction zone at a plurality of points excluding the rst and including the last of said points in the direction of flow, the reactivated catalyst introduced to said last -point being the sole catalyst introduced thereto and an increasing quantity of reactivated catalyst being introduced at each succeeding point in the direction of ow, the total quantity and temperature of said hot reactivated catalyst being suicient to supply heat to the reaction zone in amounts equal at least to a substantial proportion of the endothermic heat of the cracking reaction and thereby minimizing an otherwise decreasing temperature gradient in the direction of flow and increasing the extent of reaction which would otherwise occur in the latter portions of said reaction zone to a value more nearly equal to that occurring in the rst portions of said reaction zone.

2. A process for the endothermic catalytic conversion of hydrocarbons which comprises passing said hydrocarbons through an elongated reaction zone at conversion conditions of temperature and pressure such that the temperature would normally decrease in the direction of oW due to the endothermic reaction, introducing particulate solid catalyst from two sources as hereinafter described into said reaction zone at a plurality of points spaced in the direction of ilow for passage through said zone concurrently with said hydrocarbons, recovering conversion. products from said reaction zone, recovering from said reaction zone substantially all of the catalyst so introduced, the thus-recovered catalyst still retaining some activity, reactivating only a portion of said separated catalyst by burning carbonaceous matter therefrom in an oxygenecontaining gas at a temperature higher than said conversion temperature to form a portion of hot reactivated catalyst and a hot oxygen-free gas, separating said hot oxygen-free gas and contacting same directly with the remainder of said separated catalyst which has not been reactivated to heat the latter to a temperature above the conversion temperature, recycling the thus-heated remainder of said 23 separated catalyst Withoutreactivation. to a. plurality of said points including the rst and excluding the last of said points in the direction of ow, the um'eactivated catalyst introduced to said first point being the sole catalyst introduced thereto and a diminishing quantity of unreactivated catalyst being introduced at each succeeding point in the direction of ow, introducing the hot reactivated portion of said catalyst into the reaction zone at a plurality of points excluding the first and including the last of said points in the direction of ow, the reactivated catalyst introduced to said last point being the sole catalyst introduced thereto and an increasing quantity of reactivated catalyst being introduced at each succeeding point in the direction of ow, the total quantity and temperature of said hot reactivated and unreactivated catalyst being suicient to supply heat to the reaction zone in an amount at least equal to the endothermic heat of reaction and the said points being so spaced and the temperatures and amounts of hot unreactivated and hot reactivated catalyst introduced at each point being so proportioned as to maintain the temperature along the length of said reaction zone substantially constant.

24 3. The process of claim 2 in which the relative amounts of unreactivated and reactivated catalyst introduced at the respective points are so vproportioned as to maintain such an increasing THOMAS B. HUDSON.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,289,329 Prickett July 7, 1942 2,403,375 Kassel July 2, 1946 2,416,214 Payne Feb. 18, 1947 zo 2,418,672 Sinclair et al. Apr. 8, 1947 2,420,904 Noll May 20, 1947 2,429,161 Hudson Oct. 14, 1947 FOREIGN PATENTS u Number Country Date 411,477 Great Britain Dec. 2, 1932 Certificate of Correction Patent No. 2,518,474 August 15, 195o It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 57, for the Word Finally read Fingaly; line 60, for mained read maintained; column 5, line 43, for long read along; column 10, line 11, for in the read at the; column 11, line 6, for polymerizating read pol w'rzz'ng; line 44, for ntaural read natural; column 18, line 31, for against read again; and that the said Letters Patent should be read as corrected labove, so that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 24th day of April, A. D. 1951.

THOMAS F. MRHY,

Assistant Uommssz'oner of Patents.

THOMAS B. HUDSON 

1. A PROCES FOR THE CATALYTIC CRACKING OF PETROLEUM OIL INTO LOWER BOILING PRODUCTS WHICH COMPRISES PASSING VAPORS OF SAID OIL THROUGH AN ELONGATED REACTION ZONE AT CRACKING CONDITIONS OF TEMPERATURE AND PRESSURE SUCH THAT NORMALLY THERE WOULD BE A TEMPERATURE DECREASE IN THE DIRECTION OF FLOW DUE TO THE ENDOTHERMIC CRACKING REACTION, INTRODUCING POWDERED CRACKING CATALYST FROM TWO SOURCES AS HEREINAFTER DESCRIBED INTO SAID REACTION ZONE AT A PLURALITY OF POINTS SPACED IN THE DIRECTION OF FLOW FOR SUSPENSION IN SAID VAPORS, SEPARATING SAID LOWER-BOILING PRODUCTS FROM THE EFFLUENTS OF SAID REACTION ZONE, SEPARATING SUBSTANTIALLY ALL OF THE CATALYST SO INTRODUCED FROM THE EFFLUENTS OF SAID REACTION ZONE, THE THUS-SEPARATED CATALYST STILL RETAINING SOME ACTIVITY, REACTIVATING ONLY A PORTION OF SAID SEPARATED CATALYST BY BURNING CARBONACEOUS MATTER THEREFROM IN AN OXYGEN-CONTAINING GAS AT A TEMPERATURE HIGHER THAN SAID CRACKING TEMPERATURE TO FORM A PORITON OF HOT REACTIVATED CATALYST AND A HOT OXYGEN-FREE GAS, SEPARATING SAID HOT OXYGEN-FREE GAS AND CONTACTING SAME DIRECTLY WITH THE REMAINDER OF SAID SEPARATED CATALYST WHICH HAS NOT BEEN REACTIVATED TO HEAT THE LATTER TO A TEMPERATURE ABOVE THE CRACKING TEMPERATURE, RECYCLING THE THUS-HEATED REMAINDER OF SAID SEPARATED CATALYST WITHOUT REACTIVATION TO A PLURALITY OF SAID POINTS INCLUDING THE FIRST AND EXCLUDING THE LAST OF SAID POINTS IN THE DIRECTION OF FLOW, THE UNREACTIVATED CATALYST INTRODUCED TO SAID FIRST POINT BEING THE SOLE CATALYST INTRODUCED THERETO AND A DIMINISHING QUANTITY OF UNREACTIVATED CATALYST BEING INTRODUCED AT EACH SUCCEEDING POINT IN THE DIRECTION OF FLOW, INTRODUCING THE HOT REACTIVATED PORITON OF SAID CATALYST INTO THE REACTION ZONE AT A PLURALITY OF POINTS EXCLUDING THE FIRST AND INCLUDING THE LAST OF SAID POINTS IN THE DIRECTION OF FLOW, THE REACTIVATED CATALYST INTRODUCED TO SAID LAST POINT BEING THE SOLE CATALYST INTRODUCED THERETO AND AN INCREASING QUANITY OF REACTIVATED CATALYST BEING INTRODUCED AT EACH SUCCEEDING POINT IN THE DIRECTION OF FLOW, THE TOTAL QUANTITY AND TEMPERATURE OF SAID HOT REACTIVATED CATALYST BEING SUFFICIENT TO SUPPLY HEAT TO THE REACTION ZONE IN AMOUNTS EQUAL AT LEAST TO A SUBSTANTIAL PROPORTION OF THE ENDOTHERMIC HEAT OF THE CRACKING REACTION AND THEREBY MINIMIZING AN OTHERWISE DECREASING TEMPERATURE GRADIENT IN THE DIRECTION OF FLOW AND INCREASING THE EXTENT OF REACTION WHICH WOULD OTHERWISE OCCUR IN THE LATTER PORITONS OF SAID REACTION ZONE TO A VALUE MORE NEARLY EQUAL TO THAT OCCURRING IN THE FIRST PORTIONS OF SAID REACTION ZONE. 